EP1853635B1 - Procede et dispositif de polymerisation d'ethylene - Google Patents

Procede et dispositif de polymerisation d'ethylene Download PDF

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Publication number
EP1853635B1
EP1853635B1 EP06706488A EP06706488A EP1853635B1 EP 1853635 B1 EP1853635 B1 EP 1853635B1 EP 06706488 A EP06706488 A EP 06706488A EP 06706488 A EP06706488 A EP 06706488A EP 1853635 B1 EP1853635 B1 EP 1853635B1
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Prior art keywords
gas
propane
ethylene
polymer particles
reactor
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EP1853635A1 (fr
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Giuseppe Penzo
Cyrus Ahmadzade-Youssefi
Rainer Karer
Ulrich Nieken
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Basell Polyolefine GmbH
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Basell Polyolefine GmbH
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F10/02—Ethene
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
    • B01J8/0015—Feeding of the particles in the reactor; Evacuation of the particles out of the reactor
    • B01J8/0035—Periodical feeding or evacuation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
    • B01J8/005—Separating solid material from the gas/liquid stream
    • B01J8/006—Separating solid material from the gas/liquid stream by filtration
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
    • B01J8/18—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles
    • B01J8/24—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles according to "fluidised-bed" technique
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/34—Polymerisation in gaseous state
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F6/00—Post-polymerisation treatments
    • C08F6/001—Removal of residual monomers by physical means
    • C08F6/005—Removal of residual monomers by physical means from solid polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2208/00—Processes carried out in the presence of solid particles; Reactors therefor
    • B01J2208/00008—Controlling the process
    • B01J2208/00017—Controlling the temperature
    • B01J2208/00106—Controlling the temperature by indirect heat exchange
    • B01J2208/00265—Part of all of the reactants being heated or cooled outside the reactor while recycling
    • B01J2208/00274—Part of all of the reactants being heated or cooled outside the reactor while recycling involving reactant vapours
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2208/00—Processes carried out in the presence of solid particles; Reactors therefor
    • B01J2208/00743—Feeding or discharging of solids
    • B01J2208/00761—Discharging
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00002—Chemical plants
    • B01J2219/00004—Scale aspects
    • B01J2219/00006—Large-scale industrial plants
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F110/02—Ethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F210/16—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/582—Recycling of unreacted starting or intermediate materials
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S526/00—Synthetic resins or natural rubbers -- part of the class 520 series
    • Y10S526/92—Apparatus for use in addition polymerization processes

Definitions

  • the invention relates to a process for the polymerization of ethylene or of ethylene with further 1-olefins, in which the ethylene is polymerized in the presence of a catalyst in a gas-phase reactor and reaction gas comprising propane and unpolymerized ethylene is circulated to remove the heat of polymerization, wherein the polymer particles are discharged continuously or discontinuously from the reactor; the polymer particles are separated from the major part of the concomitantly discharged gas and the polymer particles are degassed. It also relates to an apparatus for carrying out the process.
  • Gas-phase polymerization processes are economical processes for the polymerization of ethylene and propene or for the copolymerization of ethylene or propene with other C2-C8-1-olefins.
  • Such gas-phase polymerization processes can, in particular, be designed as gas-phase fluidized-bed processes in which the polymer particles are kept in suspension by means of a suitable gas stream. Processes of this type are described, for example, in EP-A-0 475 603 , EP-A-0 089 691 and EP-A-0 571 826 , which are hereby fully incorporated by reference.
  • the polymer particles present in the fluidized bed are discharged continuously or discontinuously and conveyed pneumatically into a degassing vessel.
  • a degassing vessel Especially in the copolymerization of ethylene with further 1-olefins such as 1-butene or 1 hexene, considerable amounts of the comonomers together with further relatively high-boiling gases present in the reaction gas or liquids such as hexane remain in the polymer particles.
  • a stripping gas to remove a considerable proportion of the relatively high-boiling comonomers in the degassing vessel.
  • nitrogen is usually used for this purpose.
  • the nitrogen has to be pure nitrogen (O2 ⁇ 2 vppm, H2O ⁇ 2 vppm), which incurs not inconsiderable costs.
  • EP-A-683 176 describes the use of the reaction mixture or of constituents of the reaction mixture, preferably in a mixture with nitrogen.
  • constituents of the reaction mixture mention is made not only of ethylene and hydrogen but also of nitrogen and C1-C12-, preferably C4-C8-alkanes as inert constituents.
  • JP 60-079017 discloses degassing of the polymer particles in a downstream silo by means of inert hydrocarbons, with the hydrocarbon used for degassing having the same number of carbon atoms as the 1-olefin to be removed.
  • US 5 376 742 and WO 03/011920 disclose a process for polymerization of olefin monomer including ethylene and/or propylene with at least one alpha-olefin in a fluidized bed gas phase reactor wherein part of the effluent stream (recyle gas) from the reactor is separated and used for degassing the polymer.
  • the heavy hydrocarbons and, in WO 03/011920 additionally the monomers are removed from the gas before its use for the degassing.
  • the disadvantage of this degassing method is that the gas is taken from the recycle line and fed back to it after the degassing. Therefore the degassing cycle is highly dependent on the conditions, particularly the pressure, in the reactor. Further the heat removal from the polymerization reactor is limited by the use of nitrogen.
  • This object is achieved by a process for the polymerization of ethylene or of ethylene with further 1-olefins, in which the ethylene is polymerized in the presence of a catalyst in a gas-phase reactor to form polymer particles and reaction gas comprising propane and unpolymerized ethylene is circulated to remove the heat of polymerization, wherein
  • composition of the reaction gas are based on the conditions prevailing in the reactor and those made regarding the recycle gas are based on the composition in the recycle gas line upstream of the first separation column.
  • the present invention ensures a high heat discharge from the reactor both in the noncondensed mode and in the condensed mode and sufficient degassing of the discharged polymer particles.
  • the corresponding work-up and use of the propane used in the recycle gas for degassing the discharged polymer particles ensures a high degree of recovery of the reaction gas comprising ethylene and propane and of the stripping gas which preferably consists essentially of propane under particularly economical operating conditions.
  • ethylene recovery is also maximized by means of the present invention, since only small amounts of ethylene are removed from the recycle gas together with the discharged ethane. Further advantages of the present invention can be derived from the following description.
  • the gas-phase reactor can be any type of gas-phase reactor, for example either.a gas-phase fluidized-bed reactor or a stirred gas-phase reactor, with the use of proportions of condensed material also being possible.
  • a gas-phase fluidized-bed reactor or a stirred gas-phase reactor, with the use of proportions of condensed material also being possible.
  • Discharge from the reactor can be carried out pneumatically or with the aid of mechanical discharge systems, with pneumatic discharge being preferred.
  • discharge is achieved by means of the pressure gradient prevailing between the reactor and a downstream degassing vessel.
  • the separation of the polymer particles discharged from the reactor from the major part of the discharged gas can be carried out together with or separately from the degassing of the polymer particles by means of the propane fraction, either in terms of time or in terms of space.
  • the separation of the particles from the gas can be carried out in a first vessel and the stripping with the propane can be carried out subsequently in a second vessel.
  • the major part of the reaction gas can firstly be separated off from the particles and the degassing with propane can subsequently be carried out in the same vessel.
  • degassing of the polymer particles by means of the propane fraction and the separation of the polymer particles from the major part of the discharged gas preference is given to be effected simultaneously and/or in the same place.
  • the degassing of the polymer particles by means of the propane fraction and the separation of the polymer particles from the major part of the discharged gas is particularly preferably effected immediately after discharge from the reactor in one degassing vessel.
  • the parallel arrangement of two or more degassing vessels is obviously possible.
  • the degassing of the polymers is preferably performed counter-currently.
  • Degassing of the polymer particles according to the present invention means that the content of further 1-olefins and/or alkanes having 4 to 12 carbon atoms in the polymer particles is reduced by means of gas to a given.
  • the residual loading of the polymer with the relatively high-boiling dissolved components such as butene, hexene or hexane should be very low so as to keep the loss of hydrocarbons as low as possible. Preference is given to a residual loading of less than 2500 ppm by weight, particularly preferably less or equal 500 ppm by weight.
  • the propane used for degassing in the degassing vessel under the degassing conditions should have a partial pressure of less than 10000 Pa, preferably less than 2500 Pa, more preferably less than 500 Pa, of further 1-olefins and alkanes having from 4 to 12 carbon atoms.
  • the partial pressure proportion of 1-olefins and alkanes having from 4 to 12 carbon atoms in the propane fraction is particularly preferably less than 250 Pa, in particular less than 25 Pa mol%.
  • the corresponding total proportion of further 1-olefins and alkanes should preferably be less than 4 mol%, more preferably less than 1 mol%, more preferably less than 0.2 mol%, particularly preferably less tan 0.1 mol%, most preferably less than 0.01 mol%.
  • the propane fraction can additionally be brought to elevated temperatures by means of a heat exchanger.
  • the temperature should in this case be significantly below the softening temperature of the polymer to be degassed.
  • the proportion of ethylene in the propane fraction used in the degassing vessel should be less than 6000 Pa is preferably less than 1500 Pa, more preferably less than 750 Pa, in particular less than 300 Pa.
  • the corresponding total proportion of Ethylene in the propane fraction should be less than 4 mol%, preferably less than 1 mol%, more preferably less than 0.5 mol%, in particular less than 0.2 mol%.
  • separation techniques which may be employed here are separation by distillation and separation by means of selectively permeable membranes, without the invention being restricted to these. Rather, it is possible to use any separation unit to achieve the advantages of the process of the invention, as long as the purity according to the invention of the propane fraction can be achieved using this. Preference is given to separation by distillation. Since the degassing cycle is decoupled from the main recycling stream of the reactor the pressure in the degassing cycle can be set to higher values than in the reactor. This allows depending on the site conditions the use of cooling water to condensate the distillate instead of using a refrigeration unit to provide the necessary cooling.
  • the reaction gas can further comprise additional inert gases such as nitrogen (N2).
  • additional inert gases such as nitrogen (N2).
  • ethane is always present in varying amounts in the ethylene.
  • the proportion of propane in the reaction gas should be 30 mol% or more.
  • fresh propane can be introduced in addition to the propane fraction upstream of the degassing vessel, but this is less advantageous.
  • a maximum of 10 mol%, particularly preferably a maximum of 5 mol%, of other gases or liquids are present in addition to ethylene, further 1-olefins and propane in the reactor.
  • the reaction gas is particularly preferably free of inert gases with the exception of aliphatic hydrocarbons.
  • reaction gas consisting essentially of only ethylene, if appropriate further 1-olefins and propane.
  • propane When nitrogen is completely replaced by propane, the specific heat capacity of the recycle gas is maximized, as a result of which the recycle gas volume flow necessary for removing the heat of polymerization can be minimized.
  • peripheral apparatuses such as compressors, heat exchangers, recycle gas line, etc.
  • the amount of nitrogen is very small it is possible to pass the ethane bled off from the recycle gas directly as feed to a cracker, instead of burning it for heating purposes or flaring it.
  • the heat discharge from the gas-phase fluidized-bed reactor can be achieved exclusively by the circulated gas in the noncondensed mode. It can also be advantageous to take the reaction gas from the reactor, partly condense the reaction gas, preferably containing mainly propane, and recirculate the condensate together with or separately from the uncondensed gas, so that the reactor is operated in the condensed mode.
  • the ethylene separated off in the first separation stage is recirculated to the reactor together with other low boilers such as ethane. Furthermore, preference is given to at least part of the ethane separated off in the first separation stage being discharged from the process as a purge gas stream.
  • the removal of the fine particles (fines) from the gas entering the fist separation stage can be performed by any method.
  • the removal is preferably performed by using filters.
  • Preferred filter systems are described in Freeing according to the present invention means the fine particles are removed from the gas stream to an extend avoiding polymerization in the separation stages. Preferably the fine particles are essentially removed.
  • a process for the polymerization of ethylene or of ethylene with further 1-olefins in which the ethylene is polymerized in the presence of a catalyst in a gas-phase reactor to form polymer particles and reaction gas comprising propane and unpolymerized ethylene is circulated to remove the heat of polymerization, wherein
  • the present invention further provides as a first alternative an apparatus for carrying out the process according to any of the preceding claims comprising
  • the first alternative is preferred if a distillation is used since an evaporation of the propane fraction coming from the bottom of the second column can be avoided if the propane fraction is the top product of the second separation unit.
  • the present invention provides for the use of propane having a proportion of ethylene of less than 4 mol% and a proportion of the sum of 1-olefins and alkanes having from 4 to 12 carbon atoms of less than 4 mol%, in each case based on the total amount of gas, for degassing ethylene homopolymers or ethylene copolymers.
  • Part of this propane is obtained from the gas discharged from a gas-phase polymerization reactor together with the polymer particles.
  • Figure 1 shows the flow diagram of a polymerization plant according to a preferred embodiment of the invention having a gas-phase fluidized-bed reactor 1.
  • the gas-phase fluidized-bed reactor 1 comprises a cylindrical tube in which the fluidized bed, which usually consists of polymer particles kept in suspension in the gas phase by means of a stream of gas, is located.
  • the velocity of the reaction gas has to be high enough firstly to fluidize the mixed bed of polymer particles which is located in the tube and serves as polymerization zone and secondly to remove the heat of polymerization effectively.
  • reaction gas comprising not only a gas or a gas mixture but also condensed fluids which vaporize in the reactor into the fluidized bed.
  • the fluidized bed is usually bounded at the bottom by a gas distributor plate. At the top, the cylindrical part is usually adjoined by a widening disengagement zone which reduces the discharge of particles from the reactor 1. In an alternative embodiment, the disengagement zone can also be omitted.
  • the reaction gas leaves the reactor 1 at the upper end of the disengagement zone and is conveyed in the recycle gas line 3 via a cyclone 4 to the compressor 10b and from there via a heat exchanger 17 in which the recycle gas is cooled back to the reactor 1.
  • the recycle gas can, if appropriate, be cooled to below the dew point of one or more of the recycle gas components in the heat exchanger so as to operate the reactor with condensed material, i.e. in the condensed mode.
  • the circulated reaction gas comprises a mixture of ethylene, if desired a molecular weight regulator such as hydrogen and propane and/or further saturated hydrocarbons such as ethane, butane, pentane or hexane.
  • a molecular weight regulator such as hydrogen and propane and/or further saturated hydrocarbons such as ethane, butane, pentane or hexane.
  • further additives and auxiliaries such as metal alkyls, antistatics, catalyst poisons, etc., can also be used.
  • nitrogen in conjunction with the degassing by means of propane is less advantageous, since it can only be separated off from the ethylene again with considerable difficulty.
  • reaction gas can further comprise C3-C8-1-olefins such as propene, 1-butene, 1-pentene, 2-methylpentene, 1 hexene, 1-heptene and 1-octene as comonomers, and these can also be present in condensed form. Preference is given to a process in which ethylene is copolymerized with 1-hexene or 1-butene.
  • the constituents of the reaction gas can be fed into the gas-phase fluidized-bed reactor either directly or via the circulated reaction gas.
  • the capacity of the gas-phase fluidized-bed reactor 1 is known to be limited by the cooling capacity of the circulated reaction gas.
  • the cooling capacity is dependent not only on the heat capacity, i.e. the chemical composition, of the reaction gas but also, inter alia, on the pressure of the reaction gas or at which the (co)polymerization is carried out.
  • it is generally advisable to work at pressures of from 0.1 to 10 MPa, preferably from 1 to 8 MPa, particularly preferably from 1.5 to 5 MPa, in particular from 2 to 3 MPa.
  • the cooling capacity also depends on the reactor temperature at which the (co)polymerization in the fluidized bed is carried out.
  • temperatures of from 30 to 125°C, particularly preferably from 75 to 118°C with temperatures in the upper part of this range preferably being set for copolymers of relatively high density and temperatures in the lower part of this range preferably being set for copolymers of relatively low density.
  • the amount of catalyst introduced determines the product output.
  • the catalyst or catalysts is/are introduced via one or more catalyst metering devices 7, for example by means of the dry metering device disclosed in EP-A-226935 , which is hereby fully incorporated by reference.
  • the metered addition likewise to be carried out by means of propane, preferably by means of liquid propane, as in WO 04/092229 , which is hereby fully incorporated by reference.
  • propane is preferably likewise taken from the propane fraction.
  • catalysts it is possible to use all known types of catalyst which are suitable for olefin polymerization.
  • single-site catalysts comprise, unlike chromium and Ziegler/Natta catalysts, at least one defined organometallic transition metal compound and usually further activating compounds and, if appropriate, support and also further additives and auxiliaries.
  • Combinations of catalysts can also be used advantageously, with combinations of different single-site catalysts being preferred.
  • the catalysts can be immobilized together on a support or can be metered separately into the reactor.
  • the polymer particles usually have a mean size of from a few hundred to a few thousand microns.
  • the mean particles In the case of chromium catalysts, the mean particles have a size of from about 400 to 600 ⁇ m, and in the case of Ziegler catalysts the mean particle size is about 1500 - 2000 ⁇ m.
  • the polymer particles are taken from the reactor 1 pneumatically via one or more product offtake lines 2.
  • the product can be discharged continuously or discontinuously, with discontinuous discharge being preferred.
  • the polymer is freed of the major part of the gas carried with it in a degassing vessel 5 and is treated with purified propane which has been worked up as described in more detail below.
  • the pressure in the degassing vessel 5 is about 0.1-0.4 MPa, preferably 0.15 to 0.35 MPa.
  • the degassing by means of propane reduces the residual content of further 1-olefins and relatively nonvolatile inert gases, for example hexane, adsorbed on the polymer particles to contents of about 0.25% by weight, preferably less than 0.05% by weight.
  • the degassed polymer particles are subsequently taken from the degassing vessel 5 by means of star feeders 18 and conveyed to a degassing silo (not shown) where further degassing by means of nitrogen or as described in WO 04/047959 is carried out.
  • a further propane gas stream can be fed in as barrier gas between the star feeders 18.
  • the residence times of the polymer in the degassing vessel are between 10 minutes and 8 hours depending on the content of further 1-olefins and/or alkanes having 4 to 12 carbon atoms. Preferred are 15 minutes to 5 hours.
  • the purified gas is compressed in a compressor 10a to a pressure of from 2.0 to 4 MPa, preferably 2.3 to 3.5 MPa, and is, after condensed material has been separated off in a liquid precipitator 11, subjected to a two-stage separation by distillation.
  • a low-boiling fraction containing ethylene preferably consisting essentially of ethylene and ethane, up to 55 % of propane and possibly further low-boiling recycle gas components like hydrogen (C2 fraction) is separated off and conveyed from the top of the column via the gas return line 14 to the recycle gas line 3.
  • ethylene preferably consisting essentially of ethylene and ethane
  • propane and possibly further low-boiling recycle gas components like hydrogen (C2 fraction) is separated off and conveyed from the top of the column via the gas return line 14 to the recycle gas line 3.
  • ethane is bled off via the ethane purge line 19.
  • the ethane discharged can be fed directly as feed to a cracker. Together with the ethane further undesirable by-products otherwise accumulating in the circuit can be removed.
  • a side stream of the low boiling fraction may be fed to a further columns (not shown) to separate the propane residues and to concentrate the low boiling content like ethane, ethylene and hydrogen.
  • the bottoms from the first separation column 12 which are enriched in relatively high-boiling hydrocarbons (C3+ fraction), consisting essentially of propane, the other 1-olefins and saturated hydrocarbons, are fed via a connecting line 13 to a second separation unit configured as a separation column 15.
  • a second separation unit configured as a separation column 15.
  • propane is obtained at the top of this second separation column 15, while all heavier hydrocarbons are present in the bottoms.
  • the column is designed so that the content of higher hydrocarbons such as 1-hexene, 1-butene or n hexane is preferably less than 0.1 mol% and that of ethylene is less than 1 mol%, corresponding to 150 and 15 Pa at a degassing pressure of 0.15 MPa, respectively.
  • the dependence of the ethylene content of the propane fraction as a function of the mode of operation of the first separation column is shown in figure 2 as an example.
  • the separation columns can be exchanged.
  • the high boiling fraction containing the further 1-olefins and alkanes having 4 to 12 carbon atoms is separated in the first stage and afterwards the top product (distillate) is split into a clean propane fraction and the low boiling fraction containing ethylene and ethane.
  • the amount of propane obtained can be set in a simple manner via the power of the vaporizer of the second separation column or by a valve located between the second distillation column 15 and the degassing vessel.
  • the purity of the propane in respect of ethylene can be influenced by the power of the vaporizer of the first column, while the content of higher hydrocarbons in the propane is adjusted via the reflux ratio in the second separation column 15.
  • the temperature of the bottom product in the second separation column 15 should be below 120°C in order to allow utilising low pressure steam as heating medium and to avoid ongoing reaction with 1-olefins.
  • the temperature of the liquid bottom product is adjusted by means of the flow of distillate (C2 fraction) in the first separation column.
  • the dependence of the ethylene content of the propane fraction on the power of the vaporizer (right-hand scale) and condenser (left-hand scale) of the first separation column 12 is shown as an example in figure 2 .
  • one or both of the columns can also be replaced by a membrane separation unit or other separation unit although it is less preferred.
  • the bottom temperature of column 15 is regulated by mass flow rate of the bottom fraction. The bottom temperature should on the one hand be low enough to allow the heating of the bottom vaporizer of column 15 by low pressure steam. On the other hand very high temperature should be avoided to suppress the polymerization of ethylene and further 1-olefins with catalyst residues.
  • the propane which has been purified in this way is conveyed via the propane line 16 to the heat exchanger 17, heated to a temperature which is from 5 to 20°C below the softening point of the polymer, preferably to about 100°C, and subsequently fed into the degassing vessel 5.
  • the degassing vessel the primary degassing of the polymer particles is carried out and the stripping loop is closed.
  • the low hexene content of the propane ensures degassing of the polymer to a low residual hexene content, while the low ethylene content prevents appreciable after-polymerization and thus the formation of oligomers (gels). Particularly the quality of film products is highly decreased by such gels.
  • propane used for removal of the heat of polymerization as inert gas for the degassing of the polymer also makes it possible to achieve a high degree of recovery both of the ethylene and of the degassing agent, which is advantageous both from an economic point of view and from an ecological point of view. Furthermore, propane has a significantly greater heat capacity than nitrogen, which increases the heat discharge.
  • the 1-hexene and any hexane enriched in the bottoms from the second separation column 15 is/are recirculated via the gas return line 8 and a condensation vessel (not shown) to the reactor 1.
  • Any hexane present can subsequently be employed for metering in reaction auxiliaries such as antistatics or metal alkyls (scavengers).
  • reaction auxiliaries such as antistatics or metal alkyls (scavengers).
  • the small losses of propane which occur despite the use of the process of the invention are compensated by introduction of appropriate amounts of fresh propane into the recycle gas line 3.
  • the propane may have its source from that used for catalyst preparation and/or for catalyst feeding.
  • the purified propane can also be used for the metered addition of the catalyst.
  • propane is depressurized in the catalyst metering device 7 into the reactor 1 and thus vaporized, as described in WO 2004/092229 .
  • the propane can be used in this way in liquid form or as a gas.
  • the fine dust separated off from the reaction gas in the cyclone 4 is advantageously added to the product in the degassing vessel 5 via the fine dust line 6 or alternatively fed back into the reactor 1. In this case it is very useful to add a catalyst poison to the recycling gas before entering the cyclone ensuring that no active catalyst residues enter the degassing vessel 5.
  • Example 1 2 Catalyst Type Ziegler Chromium (Phillips) Density [kg/m 3 ] 919 942 Reactor pressure [MPa] 2,3 2.0 Reactor temperature [°C] 85 115 Degassing pressure [MPa] 0.25 0.25 1-Hexene concentration [Vol%] 3.3 0.1 Hexane concentration [Vol%] 0 5.0 Solubility [kg /kg Polymer] 0.034 0.019 Propane stream [kg/h] 3900 1500 Product Residence time [h] 3.5 1.0

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Abstract

La présente invention concerne un procédé permettant de polymériser de l'éthylène ou de l'éthylène associé à des 1-oléfines. Selon ce procédé, l'éthylène est polymérisé en présence d'un catalyseur dans un réacteur à phase gazeuse et un gaz de réaction contenant du propane et de l'éthylène non polymérisé est mis en circulation de manière à éliminer la chaleur de la polymérisation. Les particules polymères sont évacuées du réacteur en continu ou de manière discontinue; ces particules polymères sont séparées de la partie principale du gaz évacué simultanément et ces particules polymères sont dégazées. Le gaz est débarrassé des particules fines entraînées et il est séparé d'une fraction à bas point d'ébullition comprenant de l'éthylène ou d'une fraction à point d'ébullition élevé contenant également des 1-oléfines ou des alcanes présentant de 4 à 12 atomes de carbone dans une première étape de séparation, une fraction propane est détachée dans une seconde étape de séparation, cette fraction propane est utilisée pour dégazer les particules polymères évacuées du réacteur; la proportion d'éthylène dans la fraction de propane étant inférieure à 1 % molaires et la proportion des 1-oléfines et des alcanes présentant de 4 à 12 atomes de carbone dans la fraction de propane étant inférieure à 4 % molaire, dans chaque cas sur la base de la fraction propane totale. En outre, cette invention concerne un dispositif permettant de mettre en oeuvre un tel procédé. Le mode de réalisation décrit dans cette invention permet d'obtenir une importante décharge thermique du réacteur, un dégazage satisfaisant des particules polymères et une récupération du gaz de réaction évacué conjointement avec les particules polymères ainsi que le gaz utilisé pour le dégazage des particules polymères.

Claims (18)

  1. Procédé de polymérisation de l'éthylène ou de l'éthylène avec d'autres 1-oléfines, dans lequel l'éthylène est polymérisé en présence d'un catalyseur dans un réacteur à phase gazeuse (1) pour former des particules de polymère et un gaz réactionnel comprenant du propane et de l'éthylène non polymérisé est fait circuler pour éliminer la chaleur de polymérisation, dans lequel
    - les particules de polymère sont déchargées du réacteur de façon continue ou discontinue (1),
    - les particules de polymère sont séparées de la majeure partie du gaz déchargé de façon concomitante et les particules de polymère sont dégazées,
    - le gaz est libéré des particules fines entraînées,
    - le gaz est séparé d'une fraction à bas point d'ébullition comprenant de l'éthylène ou d'une fraction à point d'ébullition élevé contenant d'autres 1-oléfines ou alcanes ayant de 4 à 12 atomes de carbone dans une première étape de séparation,
    - une fraction de propane est séparée dans une deuxième étape de séparation et cette fraction de propane est utilisée pour dégazer les particules de polymère déchargées du réacteur,
    la pression partielle de l'éthylène dans la fraction de propane utilisée pour le dégazage étant inférieure à 6000 Pa et la pression partielle du total des autres 1-oléfines et alcanes ayant de 4 à 12 atomes de carbone dans la fraction de propane étant inférieure à 10000 Pa.
  2. Procédé selon la revendication 1, dans lequel les 1-oléfines sont choisies parmi le 1-butène, le 1-hexène et le 1-octène et/ou les alcanes sont choisis parmi le n-butane, le n-pentane, l'isopentane, le n-hexane et le n-octane.
  3. Procédé selon l'une quelconque des revendications précédentes, dans lequel la proportion d'éthylène dans la fraction de propane est inférieure à 0,5 % en mole, en particulier inférieure à 0,2 % en mole.
  4. Procédé selon l'une quelconque des revendications précédentes, dans lequel la pression partielle de l'éthylène dans la fraction de propane est inférieure à 750 Pa, en particulier inférieure à 300 Pa.
  5. Procédé selon l'une quelconque des revendications précédentes, dans lequel la proportion de 1-oléfines et d'alcanes ayant de 4 à 12 atomes de carbone dans la fraction de propane est inférieure à 0,1 % en mole, en particulier inférieure à 0,01 % en mole.
  6. Procédé selon l'une quelconque des revendications précédentes, dans lequel la pression de vapeur des 1-oléfines et des alcanes ayant de 4 à 12 atomes de carbone dans la fraction de propane est inférieure à 150 Pa, en particulier inférieure à 15 Pa.
  7. Procédé selon l'une quelconque des revendications précédentes, dans lequel le gaz circulant comprend du propane en une quantité d'au moins 20, en particulier d'au moins 30 % en moles.
  8. Procédé selon l'une quelconque des revendications précédentes, dans lequel un maximum de 10 % en mole, de préférence un maximum de 5 % en mole, d'autres gaz ou liquides sont présents en plus de l'éthylène, des autres 1-oléfines, de l'hydrogène et du propane dans le réacteur (1).
  9. Procédé selon l'une quelconque des revendications précédentes, dans lequel le dégazage des particules de polymère au moyen de la fraction de propane et la séparation des particules de polymère de la majeure partie du gaz déchargé sont réalisés simultanément et/ou au même endroit.
  10. Procédé selon l'une quelconque des revendications précédentes, dans lequel le gaz réactionnel est prélevé du réacteur (1), une partie du gaz réactionnel est condensée et est remise en circulation conjointement avec le gaz non condensé du réacteur ou de façon séparée de celui-ci.
  11. Procédé selon l'une quelconque des revendications précédentes, dans lequel la fraction à bas point d'ébullition séparée dans la première étape de séparation est remise en circulation dans le réacteur (1).
  12. Procédé selon l'une quelconque des revendications précédentes, dans lequel une fraction à point d'ébullition élevé contenant d'autres 1-oléfines ou alcanes ayant de 4 à 12 atomes de carbone quittant la deuxième étape de séparation est remise en circulation dans le réacteur (1).
  13. Procédé selon l'une quelconque des revendications précédentes, dans lequel au moins une partie de l'éthane séparée dans la première étape de séparation est déchargée.
  14. Procédé selon l'une quelconque des revendications précédentes, dans lequel la fraction de propane est utilisée pour l'addition mesurée du ou des catalyeur(s).
  15. Appareil pour la réalisation du procédé selon l'une quelconque des revendications précédentes, comprenant
    - un réacteur à phase gazeuse (1) contenant un lit de particules de polymère,
    - une conduite de recyclage de gaz (3) reliée au réacteur pour évacuer et remettre en circulation le gaz réactionnel comprenant du propane et de l'éthylène non polymérisé,
    - une conduite d'évacuation du produit (2) pour évacuer de façon continue ou discontinue les particules de polymère du réacteur (1), ladite conduite étant reliée à un récipient de dégazage (5) pour la séparation des particules de polymère et du gaz,
    - une unité de précipitation des particules (9) pour libérer le gaz de fines particules entraînées reliée au récipient de dégazage (5),
    - une première unité de séparation (12) pour séparer une fraction à bas point d'ébullition comprenant de l'éthylène et de l'éthane reliée à l'unité de précipitation des particules (9),
    - une deuxième unité de séparation (15) pour séparer une fraction de propane reliée au bas de la première unité de séparation (12),
    - une conduite de propane qui est reliée au haut de la deuxième unité de séparation (15) et est elle-même reliée au récipient de dégazage (5) pour permettre le dégazage des particules de polymère au moyen de la fraction de propane,
    dans lequel la première unité de séparation (12) est conçue de telle sorte que la pression partielle d'éthylène dans la fraction de propane entrant dans le récipient de dégazage est inférieure à 6000 Pa et la deuxième unité de séparation (15) est conçue de telle sorte que la proportion de 1-oléfines et d'alcanes ayant de 4 à 12 atomes de carbone dans la fraction de propane entrant dans le récipient de dégazage est inférieure à 10000 Pa.
  16. Appareil pour la réalisation du procédé selon les revendications 1 à 14, comprenant
    - un réacteur à phase gazeuse contenant un lit de particules de polymère,
    - une conduite de recyclage de gaz reliée au réacteur pour retirer et remettre en circulation le gaz réactionnel comprenant du propane et de l'éthylène non polymérisé,
    - une conduite d'évacuation du produit pour évacuer de façon continue ou discontinue les particules de polymère du réacteur, ladite conduite étant reliée à un récipient de dégazage pour la séparation des particules de polymère et du gaz,
    - une unité de précipitation des particules pour libérer le gaz de fines particules entraînées reliée au récipient de dégazage,
    - une première unité de séparation pour séparer une fraction à point d'ébullition élevé comprenant les autres 1-oléfines et/ou alcanes ayant de 4 à 10 atomes de carbone reliée à l'unité de précipitation des particules (9),
    - une deuxième unité de séparation pour séparer une fraction de propane reliée au haut de la première unité de séparation,
    - une conduite de propane qui est reliée au bas de la deuxième unité de séparation et est elle-même reliée au récipient de dégazage (5) pour permettre le dégazage des particules de polymère au moyen de la fraction de propane après passage dans une unité d'évaporation,
    dans lequel la première unité de séparation est conçue de telle sorte que la pression partielle d'éthylène dans la fraction de propane entrant dans le récipient de dégazage est inférieure à 6000 Pa et la deuxième unité de séparation est conçue de telle sorte que la proportion de 1-oléfines et d'alcanes ayant de 4 à 12 atomes de carbone dans la fraction de propane entrant dans le récipient de dégazage est inférieure à 10000 Pa.
  17. Appareil selon la revendication 15 ou 16, dans lequel la première unité de séparation et/ou la deuxième unité de séparation réalisent une séparation par distillation.
  18. Utilisation du propane qui a une proportion d'éthylène inférieure à 1 % en mole et une proportion d'autres 1-oléfines et alcanes ayant de 4 à 12 atomes de carbone inférieure à 4 % en mole, basée dans chaque cas sur la quantité totale de gaz, et a été obtenue à partir du gaz déchargé d'un réacteur de polymérisation en phase gazeuse conjointement avec les particules de polymère pour le dégazage d'homopolymères d'éthylène ou de copolymères d'éthylène.
EP06706488A 2005-02-04 2006-01-30 Procede et dispositif de polymerisation d'ethylene Active EP1853635B1 (fr)

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Families Citing this family (26)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2046843B1 (fr) 2006-08-03 2010-01-20 Basell Polyolefine GmbH Procédé pour la finition de polyoléfines
EP2123682A1 (fr) * 2008-05-20 2009-11-25 INEOS Manufacturing Belgium NV Procédé de polymérisation d'oléfine
WO2011045701A1 (fr) * 2009-10-16 2011-04-21 Sasol Technology (Proprietary) Limited Séparation de composants d'un courant d'hydrocarbures multi-composants qui comprend de l'éthylène
RU2569085C2 (ru) * 2010-07-09 2015-11-20 Юнивейшн Текнолоджиз, Ллк Расширение этилена для низкотемпературного охлаждения при рекуперации отходящего газа получения полиэтилена
WO2012175469A1 (fr) 2011-06-21 2012-12-27 Basell Polyolefine Gmbh Procédé et appareil pour décharger un polymère d'un réacteur en phase gazeuse
KR101378892B1 (ko) * 2011-07-14 2014-04-04 주식회사 엘지화학 폴리올레핀 수지의 제조방법
WO2013056979A1 (fr) * 2011-10-17 2013-04-25 Ineos Europe Ag Commande de procédé de dégazage de polymère
WO2014053443A1 (fr) * 2012-10-02 2014-04-10 Ineos Europe Ag Procédé pour améliorer les opérations d'une installation de polymérisation
EP2743278A1 (fr) 2012-12-11 2014-06-18 Basell Polyolefine GmbH Procédé de dégazage et de tamponnage de particules de polyoléfine obtenues par polymérisation d'oléfines
EP2743279A1 (fr) 2012-12-11 2014-06-18 Basell Polyolefine GmbH Procédé de traitement de particules de polyoléfine obtenues par polymérisation en phase gazeuse
WO2015128329A1 (fr) * 2014-02-26 2015-09-03 Ineos Europe Ag Procédé de polymérisation et unité de polymérisation comprenant une section de dégazage
EP3237106B1 (fr) * 2014-12-22 2018-09-12 SABIC Global Technologies B.V. Récupération d'hydrocarbures à partir d'un recyclage d'hydrocarbures
BR112017028352B1 (pt) 2015-07-31 2022-02-08 Exxonmobil Chemical Patents Inc Recuperação de monômeros não reagidos a partir de processos de polimerização de olefina
US10626195B2 (en) 2015-11-18 2020-04-21 Basell Polyolefine Gmbh Polymerization process with a partial shutdown phase
CN108602904B (zh) * 2015-12-15 2021-03-12 Sabic环球技术有限责任公司 烯烃聚合方法
GB201620525D0 (en) 2016-12-02 2017-01-18 Ineos Europe Ag Process
EP3418310B1 (fr) * 2017-06-23 2020-04-08 Borealis AG Procédé et appareil de retrait de matériau polymère à partir d'un réacteur de polymérisation d'oléfines gaz-solides
EP3438133A1 (fr) * 2017-08-04 2019-02-06 Basell Polyolefine GmbH Processus de polymérisation comprenant des particules de polyoléfine de décharge provenant d'un réacteur de polymérisation en phase gazeuse
CN108854859B (zh) * 2018-07-27 2023-08-18 中化蓝天霍尼韦尔新材料有限公司 一种悬浮液气液相反应装置及运行方法
US12103988B2 (en) * 2018-12-18 2024-10-01 Basell Polyolefine Gmbh Gas-phase process for preparing ethylene polymers
CN112745435B (zh) * 2019-10-31 2022-07-12 中国石油化工股份有限公司 聚合物淤浆向聚合物溶液的转换方法和丁基橡胶生产方法
US11820841B2 (en) * 2020-01-28 2023-11-21 Exxonmobil Chemical Patents Inc. Reducing accumulation of C6+ hydrocarbon components in polyolefin gas-phase reactors
JP7366486B2 (ja) 2020-09-07 2023-10-23 エルジー・ケム・リミテッド オリゴマーの製造方法
KR20220104418A (ko) 2021-01-18 2022-07-26 주식회사 엘지화학 올리고머 제조방법
CN115246903B (zh) * 2021-04-28 2023-09-12 中国石油化工股份有限公司 连续溶液聚合方法
JP2024007084A (ja) * 2022-07-05 2024-01-18 住友化学株式会社 ポリオレフィン製造装置及び製造方法

Family Cites Families (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2735355A1 (de) * 1977-08-05 1979-02-15 Basf Ag Verfahren zum herstellen von homo- und copolymerisaten des aethylens
DZ520A1 (fr) 1982-03-24 2004-09-13 Union Carbide Corp Procédé perfectionné pour accroitre le rendement espace temps d'une réaction de polymérisation exothermique en lit fluidisé.
JPS6079017A (ja) 1983-10-05 1985-05-04 Chisso Corp ポリオレフイン粉体中に残存する未反応オレフインの回収方法
FR2570381B1 (fr) * 1984-09-17 1987-05-15 Bp Chimie Sa Procede de polymerisation d'ethylene ou de copolymerisation d'ethylene et d'alpha-olefine en lit fluidise en presence de catalyseur a base d'oxyde de chrome
DE3544915A1 (de) * 1985-12-19 1987-06-25 Basf Ag Dosiervorrichtung zum regelbaren einbringen von rieselfaehigen, pulverfoermigen stoffen in unter druck stehende raeume
FR2666338B1 (fr) 1990-08-31 1994-04-08 Bp Chemicals Snc Procede regule de polymerisation d'olefine en phase gazeuse effectue a l'aide d'un catalyseur a base d'oxyde de chrome.
IT1246614B (it) * 1991-06-03 1994-11-24 Himont Inc Procedimento per la polimerizzazione in fase gas delle olefine
DE4217171A1 (de) 1992-05-23 1993-11-25 Basf Ag Kontinuierliches Gasphasenwirbelschichtverfahren zur Herstellung von Ethylenhomopolymerisaten und -copolymerisaten
US5376742A (en) * 1993-09-23 1994-12-27 Quantum Chemical Corporation Monomer recovery in gas phase fluid bed olefin polymerization
FR2719847B1 (fr) * 1994-05-16 1996-08-09 Bp Chemicals Snc Procédé de polymérisation d'oléfine en phase gazeuse.
BR9906019B1 (pt) * 1999-12-30 2012-02-22 processo para a polimerização e copolimerização de monÈmeros olefìnicos em reatores fase gás.
GB0118609D0 (en) 2001-07-31 2001-09-19 Bp Chem Int Ltd Degassing process
ATE364436T1 (de) * 2002-11-22 2007-07-15 Basell Polyolefine Gmbh Sichere entfernung von flüchtigen, oxidierbaren verbindungen aus partikeln, insbesondere aus polymerpartikeln
DE10317533A1 (de) * 2003-04-16 2004-11-04 Basell Polyolefine Gmbh Verfahren zur diskontinuierlichen Katalysatordosierung in einen Gasphasenwirbelschichtreaktor

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